1,1,3-trimethyl-5-hydroxymethyl-3-(4-hydroxymethyl phenyl)indane

ABSTRACT

A composition of matter comprising at least one compound selected from the group consisting of:   AND   WHEREIN N IS A POSITIVE INTEGER; R1, R2 and R3 are methyl; R4, R5, R6 and R7 are hydrogen; R8 is   AND R9 and R10 are aliphatic or aromatic.

United States Patent [1 1 Wilson n11 3,859,364 145] Jan.7,1 975 1l,1,3-TRIMETHYL-S-HYDROXYMETHYL-S- (4-HY DROXYMETHYL PHENYL)INDANE [75]Inventor: John Charles Wilson, Rochester,

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Apr. 3, 1973 21 Appl. No.: 347,608

Related U.S. Application Data [62] Division of Ser. No. 180,114. Sept.13, 1971,

abandoned.

[56] References Cited UNITED STATES PATENTS 7/1956 Petropoulas 260/619 F4/1961 Petropoulas et al 260/619 F OTHER PUBLICATIONS Kitamagi et 211.,Chem Abstracts," Vol. 64, pl 8108C Primary Examiner-Joseph E. EvansAssistant Examiner-David B. Springer Attorney, Agent, or Firm-A. l-l.Rosenstein [57] ABSTRACT A composition of matter comprising at least onecompound selected from the group consisting of:

R3 X\ l 1101110 I V CHzOH and R t 1 -CHI CH1-R5- J i L R7 R5 [1 whereinn is a positive integer; R, R and R are methyl; R", R R and R arehydrogen; R is o o I o 0 and R and R are aliphatic or aromatic.

1 Claim, No Drawings 1,1 ,S-TRIMETHYL-S-HYDROXYMETHYL-3-(4-HYDROXYMETHYL PHENYLHNDANE This is a division of application Ser. No.180,114, filed Sept. 13, 1971, now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to hydroxymethyl-substituted phenylindans and polymers thereofand to the preparation of these condensants and polymers.

2. Description of the Prior Art There is a continuing demand for lowcost filmforming materials with improved physical properties which canbe used as supports for photographic elements. Many of the currentlyavailable film-forming compositions that exhibit good physicalcharacteristics are commercially unattractive owing to the cost of thecomponent ingredients or the difficulty of the manufacturing conditions.

The compound l,1,3-trimethyl--carboxy-3-(4- carboxyphenyl)indan is acommercially available material, generally referred to as phenylindandicarboxylic acid or, abbreviated, PIDA. Means for the preparation ofPIDA have been disclosed by Petropoulous in, for example, U.S. Pat. Nos.2,780,609; 2,830,966 and 2,873,262. U.S. Pat. No. 2,780,609 describesthe use of PIDA as a plasticizer for vinyl chloride polymers. U.S. Pat.No. 2,830,966 relates to polyester resin compositions comprising anunsaturated polyester resin and a polymerizible compound containing avinylidene group, wherein the polyester resin is prepared by reacting apolyhydric alcohol with an alpha, betaunsaturated polycarboxylic acidand PIDA. U.S. Pat.

SUMMARY OF THE INVENTION The present invention compriseshydroxymethylsubstituted phenylindans and polyesters and polyurethanesprepared therefrom. More particularly, the

present invention comprise a composition of matter comprising at leastone compound selected from the group consisting of and (13) a R3 R1 r 1cml i H cn2-R 'R7 R5 In in R1 wherein n is a positive integer;

R R and R are methyl and R, R5, R and R are hydrogen.

and R and R are aliphatic or aromatic.

The polymers are useful in the manufacture offibers, lacquers,adhesives, molding resins, sheets, engineering plastics orsubbinglayers. In particular, these polymers are useful as photographic filmsupports.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As stated above, the novelcondensants andpolymers of this invention respectively have thefollowing structures:

. J s R 11 As used here, n is a positive integer and preferably has avalue of at least about 15. R, R and R are methyl and R R R and R arehydrogen.

wherein R and R are aliphatic or'aromatic moieties. More specifically, Rand R can be radicals selected from the group consisting of alkyleneradicals of from 2 to 10 carbon atoms, such as ethylene, tetramethylene,pentamethylene, octamethylene, nonamethylene and the like; aryleneradicals, such as 0-, m-, or pphenylene, naphthalenediyl, oranthracenediyl, unsubstituted or substituted with radicals such ashalogen, ni-

tro, cyano, alkyl of l to 6 carbon atoms or alkoxy of l to 6 carbonatoms; arylenebisalkylene radicals wherein the alkylene portion has 1 to6 carbon atoms, such as phenylenedimethylene, phenylenediethylene,naphthalenediyldimethylene, naphthalenediyldiethylene and the like;cycloalkylene radicals, such as cyclopentylene, cyclohexylene,norbornanediyl; alkylenebisarylene radicals where the alkylene portioncontains 1 to 12 carbon atoms, such as ethylene, trimethylene,hexamethylene, decamethylene, dodecamethylene, and the arylene portionis as defined above; alkylidenebisary- 3 lene radicals where thealkylidene portion contains 1 to 12 carbon atoms, such as ethylidene,allylidene, hexylidene and the like, and the arylene portion is asdefined abovegand aralkylene radicals where the arylene and alkylcneportions areas defined above.

The radicals R and R can also be units having the formula:

wherein R R R R, R, R and R are as described above, or R and R can bepresented by the formula:

2,2-dimethyl-4-oxofur-3-yl]ethyl and the like; cycloalkyl radicals offrom 4 to 6 carbon atoms, such as cyclohexyl; and aromatic radicalshaving from 6 to 20 carbon atoms, such as phenyl,'3,4-dichlorophenyl,2,4- dichlorophenyl. R and R taken together with the carbon atom towhichthey are attached can represent a monocyclic, polycyclic, orheterocyclic moiety having from 4 to 15 atoms in the ring system.

Dicarboxylic compounds which can be employed to advantage in preparingpolyesters from the dihydroxymethyl compounds of this inventionincludesuccinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid,sebacic acid, 2-methyladipic acid, diglycolic acid,

thiodiglycolic acid, fumaric acid, cyclohexane-l,3- dicarboxylic acid,cyclohexane-l,4-dicarboxylic acid, cyclopentane-l,3-dicarboxylic acid,2,5-norbornanedicarboxylic acid, (the above-described acids being usefuleither as the cis or trans form), Phthalic acid, isophthalic acid,terephthalic acid, tbutylisophthalic acid, phenylenediacetic acid,phenylenedipropionic acid, 2,6- naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5- naphthalenedicarboxylic acid, l,7-

naphthalenedicarboxylic acid, 4,4-diphenic acid, 4,4.-

sulfonyldibenzoic acid, 4,4 '-oxydibenzoic acid, binaph-,

thyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, and9,lO-triptycenedicarboxylic acid. I

Although the dicarboxylic acids useful in the practice of this inventioncan be employed in the free acid form, 1

itis often more advantageous to utilize a bifunction'al derivative. Forexample, the corresponding acid anhydrides may beused where they areavailable. Other useful bifunctional equivalents include the lowermonohydric alcohol or phenyl esters of dicarboxylic acids and thedicarboxylic acid halides, e.g., the chlorides or bromides.

The molecular weight of the linear condensation polymers of thisinvention can vary over wide ranges; it has been found that polymershaving a molecular weight of at least about 10,000 are useful. Compoundshaving. a molecular weight from about 30,000 to 100,000 are particularlydesirable. The compounds of this invention are further characterized bytheir'inherent viscosities. Generally, the subject film-formingpolymers. have an inherent viscosity of about 0.1 to about 0.8 and thepolymers preferred as supports for photographic elements have aninherent viscosity of about 0.5 to about 0.8. The inherent viscositiesare measured at 25C in 1:1 (by wt.) phenol: chlorobenof solution unlessotherwise specified.

Instrument Products Division.

Film-forming as used in this invention refers to a material which willprovide a self-supporting film of the material when cast or extruded,for example, when cast in sheets of from 1 to '7 mils thickness.

It is appreciated, of course, that the physical properties of the broadclass of polymers of this invention, such as, for'example, the glasstransition temperature (Tg), yield strength, break strength, Youngsmodulus and the like, can be varied over a wide range. Polymers withproperties in a particular range can be easily obtained by judiciousselection of appropriate diol and dicarboxylic components and suitablemixtures thereof. The proper choice and proportions of the monomericcomponents can be determined by test procedures well-known to thoseskilled in the art of making condensation polymers. I

As indicated in the general formula set out hereinabove, the linearcondensation polymers of this invention include polyesters,polyurethanes and mixed polyester-polyurethane's. Generally, anyprocedure known in th'e art for making linear .condensation polymers canbe used in preparing the polymers of this inventionJThe following areexamples of processes that may be utilized to produce the linerpolymersof this invention.

a. The interfacial procedure can be utilized to make the polymers byconverting the diol to the bischloroformate. The preferred time ofreaction is a function of all other variables and, as such, is 'govemedby the viscosity desired for the polymer. Generally, the reaction can bemonitored by sampling and thus the preferred polymerization time chosen.A variety of solvents may be employed to provide a broad range oftemperatures and solubilities as desired. Suitable solvents include thechlorinated hydrocarbons such as, for example, chloroform,'dichloroethane, propylene dichloride, dichlorobenzene and the like.

b. Polymers, accordingto this invention, can be prepared by a solutionprocedure whereby the reactants c. The ester interchange procedure ofsynthesizing polymeric esters both by the melt process and the powderprocess can advantageously be used to make the polyesters of thisinvention, in particular, the powder process can be used advantageouslywhen the first stage polymers can be crystallized. In a preferredembodiment, these techniques may be used in combination with a solventcrystallization step to afford filmforming polyesters having improvedphysical properties. The solvent crystallization procedure generallyinvolves contacting melt process polymer with a solvent at embienttemperatures. Suitable solvents include acetone, 2-pentanone, ethylacetate, acetic acid, toluene and the like. The treated material isseparated from the solvent by any conventional procedure and put throughthe powder process. The melt process is advantageously conducted in thepresence of a catalytic agent. Useful catalysts for thetransesterification reactions include the carbonate, oxide, hydroxide,hydride and alkoxide of an alkali metal or an alkaline earth metal, acompound of a Group IVA metal of the Periodic Table, e.g., titaniumisopropoxide, organometallic halides and complex alkoxides such asNaHTi(OC H and the like.

The film-forming materials of this invention can be generally extrudedor cast into flexible supports and used in various layer arrangementsand structural combinations. Generally, the flexible supports preparedfrom the polymers of this invention are treated by any convenient methodto improve the adhesion of superimposed coatings or layers. Usefulprocedures include subbing with conventional subbing agents for polymersupports, contacting with a chemical agent such as sulfuric acid,electron bombardment, and the like. The film-forming polymers of thisinvention are used to advantage as flexible supports for photographicsilver halide and other lightsensitive systems as well as formulti-layer elements used in color photography and diffusion transferprocesses.

The following examples are included for a further understanding of theinvention. It should be understood that where equations are given, theyrepresent the overall reaction described in the particular examplewithout regard to possible mechanism.

EXAMPLE I Synthesis of 1,1,3-Trimethyl5-hydroxymethyl-3-(4-hydroxymethylphenyl)indan from1,1,3-Trimethyl-5-carboxy-3-(4-carboxyphenyl)indan and Lithium AluminumHydride To a mixture of 18.2g (0.48 mole) of lithium aluminum hydride in200 ml of dry tetrahydrofuran under nitrogen was added a solution of32.44g (0.10 mole) of 1,1,3-trimethyl-5-carboxy-3-(4-carboxyphenyl)indanin 400 ml of dry tetrahydrofuran over a 30 minute period maintaining areaction temperature of 5l-55C. The mixture was stirred for anadditional hour whereupon 200 ml of methanol were slowly added. Themixture was then poured into ice cold dilute sulfuric acid and filtered.The damp solid was dissolved in 150 ml of ethanol and filtered. To thehot filtrate was added 175 ml of water. On cooling, an oil formed whichcrystallized.,This solid was collected and dried to give 21.0g

of material; mp 108l 13C. A portion of this material (8.4g) wasrecrystallized again from 500 ml of 1:1 ligroinzbenzene solution giving5.7g of material; mp

M. Wt. 296.4g. Found: C, 80.8; H, 8.3; M. Wt., 296g.

l08-ll1C. IR and NMR data were consistent with the proposed structure.

Analysis calculated for C H O C, 81.04; H, 8.16; M. Wt., 296.4g. Found:C, 80.7; H, 8,5; M. Wt., 299g.

CH1 (1) THF on. Homo Q-cmou 2 i i CH: CH:

EXAMPLE 11 Synthesis of 1,1,3-Trimethyl-5-hydroxymethyl-3 (4-hydroxymethylphenyl)indan from1,1,3-Trimethyl-5-carbomethoxy-3-(4-carbomethoxyphenyl)indan and Sodiumbis 2-methoxyethoxy)-aluminum Hydride To 510 ml (1.36 moles) ofa 54percent refluxing solution of sodium bis (2-methoxyethoxy)aluminumhydride in benzene was added a solution of 240g (0.68 1

mole) of 1,1,3-trimethyl-5-carbomethoxy-3-(4- carbomethoxyphenyl)indanin 800 ml of benzene over a 1.17 hour period. Reflux was maintained foran additional 2 hours followed by cooling. To the cooled solution wasadded 250 ml of water over a 20 minute period, followed by 5 minutes ofadditional stirring. The mixture was filtered, the water layer separatedfrom the filtrate and the organic layer'dried over sodium sulfate. Thiswas followed by filtration and concentration of the filtrate. Theresidue was then treated with 1000 ml of refluxing 10 percent sodiumhydroxide solution for 2 hours, cooled and isolated as a grease. Thisgrease gave crystals when slurried in ether which were collected,

washed with water and dried. This material (49.5g) was recrystallizedfrom 500 ml of benzene giving 37.3g of material; mp 1l8.5l 19.5C. IR andNMR data agreed with the proposed structure.

Analysis Calculated for C H O C, 81.04; H, 8.16;

CH3 CH3 EXAMPLE m Polymerization of 1,1,3-Trimethyl-5-hydroxymethyl3-(4-hydroxymethylphenyl)indan and Terephthaloyl Chloride A solution of 406g(0.02 mole) of terephthaloyl chloride and 5.93g (0.02 mole) ofl,1,3-trimethyl-5- hydroxymethyl-3-(4-hydroxymethylphenyl)indan in 50 mlof dry pyridine was heated at reflux for two hours. The solution wasthen precipitated in 1500 ml of methanol and the polymer was collectedand dried.

The inherent viscosity of the polymer was measured in a 1:1 (wt.)phenolzchlorobenzene solution at a concentration of 0.25g/100 ml.solution at 25C and found to be 0.18. The glass transition temperaturewas determined by means of a DuPont 900 Differential ScanningColorimeter at 10C per minute in nitrogen and found to be 136C.

O i0 I EXAMPLE V Polymerization of 1,1 ,3-Trimethyl-5-hydroxymethyl-3-(4'hydroxymethylphenyl)indan and Methylenedi-p-phenyl Diisocyanate Asolution of 6.26g (0.025 mole) of methylenedi-pphenyl diisocyanate and7.41g (0.025 mole) of 1,1,3-

trimethyl-5-dich1orobenzene was heated at 7590C forl hour with acatalytic amount of dibutyltin oxide.

The polymer precipitated at this time, and the mixture on out n i Ii ClThe inherent viscosity of the polymer, determined as in Example lll, was0.55 and the glass transition tem- EXAMPLE IV 30 perature was 114C. v

110cm l- Q-cmbn uOCN-CH;.NCO- n A v 0 ll cm I I I": H 'ocn,

Example lll was repeated except that l,l',3-trimethyl-5-carboXy-3-(4-Carb0xyphenyl)indan dichloride was substituted on anequimolar basis for the terephthaloy l chloride employed therein. Theinherent viscosity of the polymer was 0.18 and the glass transitiontemperature was 181C.

onion o CH: CH

CH3 CH3 n is a positive integer.

. the methylenedi-p-phenyl diisocyanate employed n is a positiveinteger.

- EXAMPLE V1 Example V was repeated except that hexamethylenediisocyanate was substituted on an equimolar basis for l n I-ICltherein. The inherent viscosity was found to be 0.28 and the glasstransition temperature was 21C.

EXAMPLE VII Example V was repeated except that tolylene-2,4-diisocyanate was substituted on an equimolar basis for themethylenedi-p-phenyl diisocyanate employed therein. The inherentviscosity was found to be 0.18 and the glass transition temperature was135C.

. EXAMPLE VIII Preparation of a Polyurethane Film by Solvent-casting.

A sample of polymer from Example V was dissolved in tetrahydrofuran,filtered and coated on a Teflon spray-coated glass plate. After drying,a self-supporting colorless film was formed.

EXAMPLE IX A strip of film from Example VIII was treated with anactivated gas by the process of Example IV of Belgian Pat. No. 736,993for about seconds using nitrogen trioxide as both the activator andreactive. gases. The strip was then coated with a conventional gelatinsilver halide emulsion. The coating, after drying, had fair adhesion.

Generally, the film-forming materials of this invention can besolvent-cast or melt-extruded into sheets or films as useful flexiblesupports which can be utilized in various layer arrangements andstructural combinations. Generally, the flexible supports of thisinvention are treated by any convenient method to improve the adhesionof superimposed coatings or layers. Useful procedures includesub-coating with either aqueous subbing systems, such as latexes or withorganic subbing systems comprising solvent-soluble polymers in aqueousor organic solvents or in solvent mixtures, contacting with a chemicalagent, such as sulfuric acid, electron bombardment and the like.

Films prepared from the linear condensation polymers of this inventionare useful as flexible supports for photographic silver halide emulsionsand other-lightsensitive systems that do not contain halides. Polymericfilms, according to this invention, are also desirable as supports formultilayer elements used in color photography and in diffusion transferprocesses.

Film supports prepared from polymers of this invention are compatiblewith a wide variety of materials employed as binding agents inphotographic silver halide emulsions. Useful binding agents includegelatin, synthetic polymeric compounds, such as dispersed vinylcompounds, such as in latex form and mixtures of gelatin and othersynthetic polymeric compounds. The polymers of this invention findfurther use as supports for light-sensitive colloid layers such as areused in image transfer processes, in lithography, and the like. Thedimensional stability of the subject polymers make them suitable assupports for photoresists such as those utilized in the preparation ofprinted circuits, and the like.

Polymeric compositions, according to this invention, are advantageouslyprepared by standard techniques using well-known industrial processes.The compounds employed in making the polymers of this invention areprepared from readily available, inexpensive materials. A furtheradvantage of the polymers of this invention is that they may be readilyformed into film using procedures consistent with commercially availableequipment.

The invention has been described in detail with particular reference topreferred embodiments thereof,

but it will be understood that variations and modifications can beeffected within the spirit and scope of the invention.

What is claimed is:

1. A compound having the formula IIOHQC cn on UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE 0F CORREC'HCN PATENT NO. 3,859,36 i

DATED 1 January 7, 1975 INVENTOR(S) I John C. Wilson It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line Column 2, line and 15, insert on lines i7- i9 Column 5,line [SEAL] 57, comprise should read --comprises-- l3, before theformula appearing on lines 1 4 -R is--; line #6, before the formulaappearing insert "R is--.

12, "embient" should read --ambient--.

C. MARSHALL DANN (0 mm issimu'r of Parents and Trademarks RUTH C. MASONArresting Officer

1. COMPOUND HAVING THE FORMULA